1. Field of the Invention
The present invention relates to an olefin polymerization catalyst and to an olefin polymer production process. More specifically, the invention relates to a catalyst and process for production of olefin polymers with excellent moldability, using a solid catalyst component comprising a combination of a specifically treated clay compound and a metallocene compound.
2. Background Art
In recent years, metallocene catalysts with excellent polymerizing properties that give olefin polymers with a narrow composition distribution have been developed. Such catalysts, however, have generally had a drawback of poor moldability of products due to a very narrow molecular weight distribution thereof.
Olefin polymerization processes aimed at improving moldability have therefore been proposed. As examples there may be mentioned a process of combining a plurality of metallocene compounds with different extension reaction rate constants and termination reaction rate constants (Japanese Patent Laid-Open Publication No. 60-35008), a process of using a metallocene compound having a ligand with a special constrained geometric structure (Japanese Patent Laid-Open Publication No. 3-163008), and processes of combining metallocene-type catalysts and Ziegler-type catalysts using alumoxanes as an activator (Japanese Patent Laid-Open Publication No. 63-501369, Japanese Patent Laid-Open Publication No. 1-503715 and Japanese Patent Laid-Open Publication No. 3-203903). However, while such methods do provide some improving effects, their effects are still inadequate so that further improvement is desired.
On the other hand, because methylalumoxane used with metallocene catalysts is very expensive, olefin polymerization processes have been proposed that use no methylalumoxane. For example, there is known a process using a clay compound (Japanese Patent Laid-Open Publication No.5-301917). There have also been disclosed processes of combining a metallocene compound with a non-metallocene transition metal compound, for the purpose of improved moldability (Japanese Patent Laid-Open Publication No. 6-136046 and No. 9-132613). To the knowledge of the present inventors, however, all of these processes still provide inadequate effects of improved moldability.
It is therefore an object of the present invention to provide an olefin polymerization catalyst and process which allow production of olefin polymers with excellent moldability, and exhibiting excellent activity.
The present invention offers a solution to the aforementioned problems by using a specific solid catalyst component comprising a combination of a specifically treated clay compound and a metallocene compound.
That is, the olefin polymerization catalyst according to the present invention is characterized by comprising the following component (A) and component (B);
component (A): a solid catalyst component comprising the following component (A-1) and component (A-2).
component (A-1): a solid component obtained by contacting the following component (A-1-1), component (A-1-2) and component (A-1-3).
component (A-1-1): an ion-exchangeable layered silicate
component (A-1-2): a magnesium compound
component (A-1-3): a titanium compound
component (A-2): a metallocene-type transition metal compound
component (B): an organic aluminum compound.
The olefin polymer production process according to the present invention is characterized by contacting an olefin with the aforementioned olefin polymerization catalyst for its polymerization.
According to the invention, there are provided polymers with excellent moldability due to a wider molecular weight distribution (i.e. a larger ratio Mw/Mn between weight-average molecular weight (Mw) and number-average molecular weight (Mn) (Q value)) and a larger FR and melt tension (MT), compared to olefin polymers produced by polymerizing olefins in the presence of catalysts using conventional metallocene-type transition metal compounds.
[Olefin Polymerization Catalyst]
The olefin polymerization catalyst according to the present invention comprises component (A) and component (B). Here, xe2x80x9ccomprisesxe2x80x9d means not only combinations of the indicated component (A) and component (B) alone, but also encompasses combinations of adjuvant components other than component (A) component (B) but for the same purpose, that are added to component (A) and component (B).
 less than Component (A)/solid Catalyst Component greater than 
Component (A) is a solid catalyst component comprising the following component (A-1) and component (A-2). Here as well, xe2x80x9ccomprisesxe2x80x9d not only means combinations of the indicated component (A-1) and component (A-2) but also encompasses combinations thereof with adjuvant components for the same purpose.
 less than  less than Component (A-1) greater than  greater than 
Component (A-1) is a solid component obtained by contacting the following component (A-1-1), component (A-1-2) and component (A-1-3), or if necessary a solid component obtained by further contacting component (A-1-4) therewith.
The term xe2x80x9ccontainingxe2x80x9d as used herein is intended to mean not only that components (A-1-1), (A-1-2), (A-1-3) and, if desired, (A-1-4) are brought into contact with each other, but also that component (A-1-2) obtained by contacting an inorganic magnesium compound with a titanium compound such as (A-1-3) is brought into contact with component (A-1-1) and component (A-1-4) to obtain component (A).
Component (A-1-1)
Component (A-1-1) is an ion-exchangeable layered silicate.
The ion-exchangeable layered silicate used for the invention is a silicate compound having a crystalline structure wherein planes constructed by ion-bonding, etc. are stacked together in parallel by weak bonding, the ions contained in which are exchangeable. Ion-exchangeable layered silicates are for the most part produced naturally as the major components of primarily clay minerals, but these ion-exchangeable layered silicates are not particularly limited to natural products and may be artificially synthesized substances.
As specific examples of ion-exchangeable layered silicates there may be mentioned the following publicly known layered silicates listed in xe2x80x9cClay Mineralogyxe2x80x9d by Haruo Shiramizu, Asakura Shoten Publications (1995) and elsewhere: (a) the kaolin group, for example dickite, nacrite, kaolinite, anoxite, metahalloysite, halloysite, etc., (b) the serpentine group, for example, chrysotile, lizardite, antigorite, etc., (c) the smectite group, for example montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite, stevensite, etc., (d) the vermiculite group, for example vermiculite, etc., (e) the mica group, for example mica, illite, cerisite, glauconite, etc., and (f) others, for example attapulgite, sepiolite, palygorskite, bentonite, pyroferrite, talc, chlorite, etc. These may be used to form mixed layers as well. Preferred among these are smectites such as montmorillonite, sauconite, beidellite, nontronite, saponite, hectorite and stevensite, bentonite and teniolite, vermiculites such as vermiculite, and micas such as mica, illite, cerisite and glauconite.
The ion-exchangeable layered silicate preferably has a volume of 0.1 cc/g or greater, and especially 0.3-5 cc/g, of pores with a radius of at least 20 Angstroms as measured by the mercury injection method.
The ion-exchangeable layered silicate can be used directly without any particularly special treatment, but it may be subjected to chemical treatment for removal of impurities adhering to the surface, for increase of the surface area, for control of the interlayer distance or for conversion of the crystal structure of the clay. Specifically there may be mentioned acid treatment, alkali treatment, salt treatment, organic substance treatment, etc. Acid treatment and salt treatment are preferred.
For salt treatment, at least 40% and preferably at least 60% of the exchangeable metal cations contained in the ion-exchangeable layered silicate prior to treatment are preferably ion-exchanged with dissociated cations of the salt. The salt used in treatment is preferably a salt comprising a cation of an atom of Group 2-14 and an anion selected from halogen atoms, inorganic acids and organic acids. For acid treatment, the treatment is preferably carried out with hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid or the like. The treatment conditions are not particularly restricted, but normally the salt and acid concentrations are 0.1-30 wt % and the treatment temperature is 0-100xc2x0 C.
According to the invention, it is preferred that the adsorbed water and interlaminar water in the ion-exchangeable layered silicate be normally removed prior to use. Here, adsorbed water is water adsorbed onto the surface of the ion-exchangeable layered silicate particles, and interlaminar water is water present between the crystal layers. The method of dehydration the ion-exchangeable layered silicate is not particularly restricted, and heated dehydration, heated dehydration under a gas stream, dehydration under reduced pressure, azeotropic distillation with an organic solvent, etc. may be employed. Heating is carried out at 100xc2x0 C. or above and preferably 150xc2x0 C. or above, but preferably not at conditions which destroy the structure. It is therefore preferred for the moisture content to be no greater than 3 wt % preferably no greater than 1 wt %, and more preferably no greater than 0.5 wt %. as measured after drying for 2 hours under conditions of 200xc2x0 C., 1 mmHg pressure.
Component (A-1-2)
(A-1-2) of the invention is a magnesium compound. A xe2x80x9cmagnesium compoundxe2x80x9d according to the invention is preferably one which is either soluble or dispersible itself in any of the catalyst preparation processes according to the invention. (Here, xe2x80x9csoluble itselfxe2x80x9d includes compounds solubilized by complexing agent treatment or other treatment of the compound itself.)
Specific preferred examples of component (A-1-2) include (I) organic magnesium compounds, (II) contact solutions of inorganic magnesium compounds and titanium compounds (A-1-3), and (III) contact solutions of inorganic magnesium compounds and electron donating compounds.
(I) First, for the organic magnesium compound of the invention there may be used a publicly known organic magnesium compound having at least one Mgxe2x80x94C bond. It is preferably a dialkyl(aryl) magnesium compound represented by the general formula R1R2Mg or a Grignard compound represented by the general formula R3MgX. Here, R1, R2 and R3 are hydrocarbon residues of 1-20 carbon atoms that may be the same or different, and X is a halogen. Specifically, (a) compounds represented by the general formula R1R2Mg include dimethylmagnesium, diethylmagnesium, di-n-propylmagnesium, di-i-propylmagnesium, di-n-butylmagnesium, di-s-butylmagnesium, di-t-butylmagnesium, diamylmagnesium, dihexylmagnesium, dicyclohexylmagnesium, diphenylmagnesium, butylethylmagnesium, etc.; (b) compounds represented by the general formula R3MgX include methylmagnesium chloride, methylmagnesium bromide, methylmagnesium iodide, ethylmagnesium chloride, ethylmagnesium bromide, n-propylmagnesium chloride, i-propylmagnesium chloride, n-butylmagnesium chloride, s-butylmagnesium chloride, t-butylmagnesium chloride, amylmagnesium chloride, isoamylmagnesium chloride, hexylmagnesium chloride, cyclohexylmagnesium chloride, phenylmagnesium chloride, phenylmagnesium bromide, etc. Any of these within each group and/or of different groups may be mixed together, or they may be in complexes with other compounds as compound salts. Preferred for use as complexing agents are organic metal compounds of Li, Be, B, Al and Zn.
The organic magnesium compound is usually contacted with the other components in a state of solution or suspension in a solvent. The solvent used for the organic magnesium compound of the invention may be aliphatic or aromatic hydrocarbons, or ethers. Specific examples thereof include (a) hydrocarbon compounds of 4-20 carbon atoms such as butane, pentane, hexane, heptane, octane, decane, cyclohexane, benzene, toluene, xylene, etc. and (b) ethers of 2-20 carbon atoms such as dimethyl ether, diethyl ether, diisopropyl ether, dibutyl ether, diisoamyl ether, epichlorhydrin, tetrahydrofuran, dioxane, anisole, diphenyl ether, etc. These solvents may also be used in combinations of two or more.
(II) Another specific example of (A-1-2) of the invention is a contact solution of an inorganic magnesium compound and a titanium compound (component (A-1-3)).
The magnesium compound used may be a publicly known magnesium compound. Specifically there may be mentioned (a) magnesium dihalides, for example MgF2, MgCl2, MgBr2, MgI2, etc.; (b) magnesium alcoholates, for example Mg(OEt)2, Mg(OBu)2, Mg(OPh)2, etc.; (c) halomagnesiumoxy compounds, for example Mg(OH)Cl, Mg(OEt)Cl, Mg(OPh)Cl, etc.; (d) organic acid magnesium salts, for example Mg(OCOCH3)2, Mg(OCOC17H35)2, Mg(OCOC6H5)2, etc.; (e) inorganic acid magnesium salts and other compounds, for example Mg(OH)2, MgO, MgCO3, MgSO4, etc. These may also be used in admixture with each other, or may be used as complexes with other compounds in the form of compound salts. Preferred among these are (a) magnesium dihalides and (b) magnesium alcoholates.
As titanium compounds there may be mentioned compounds represented by the general formula Ti(OR4)4xe2x88x92kXk (where R4 is a hydrocarbon residue, preferably with about 1-10 carbon atoms, X represents a halogen, and k represents a number such that 0xe2x89xa6kxe2x89xa64). Specifically there may be mentioned TiCl4, TiBr4, Ti(OC2H5)Cl3, Ti(OC2H5)2Cl2, Ti(OC2H5)3Cl, Ti(OiC3H7) Cl3, Ti(OnC4H9)Cl3, Ti(OnC4H9)2Cl2, Ti(OnC4H9)3Cl, Ti(OiC4H9)Cl3, Ti(OsecC4H9)Cl3, Ti(OtC4H9)Cl3, Ti(OC5H11)Cl3, Ti(OC6H13) Cl3, Ti(OC8H17)Cl3, Ti(OcC6H11)Cl3, Ti(OC6H5)Cl3, Ti(OnC4H9)Br3, Ti(OC2H5)Cl4, Ti(OnC3H7)4, Ti(OiC3H7)4, Ti(OnC4H9)4, Ti(OnC6H13)4, Ti(OnC8H17)4, Ti(OCH2CH(C2H5)C4H9)4, etc.
As titanium compounds there may be used the polytitanic acid esters represented by the following general formula. 
where R5 represents the same or different hydrocarbon residues, preferably with 1-10 carbon atoms. Especially preferred are aliphatic hydrocarbon residues of 2-6 carbon atoms. The value of m is preferably selected so that the polytitanic acid ester is liquid either itself or in solution form, and usually represents a number such that 2xe2x89xa6mxe2x89xa610.
Specific examples of such compounds include isopropyl polytitanate, normal-butyl polytitanate, normal-hexyl polytitanate and 2-ethylhexyl polytitanate.
There may also be used trivalent titanium compounds represented by the general formula Ti(OR6)3xe2x88x92nXn (where R6 is a hydrocarbon residue, preferably with about 1-10 carbon atoms, X represents a halogen, and n represents a number such that 0xe2x89xa6nxe2x89xa63). Specific examples of such titanium compounds include TiCl3, TiBr3, Ti(OC2H5)Cl2, Ti(OC2H5)3, etc. These may also be used in admixture with each other.
Preferred among these are alkoxy group-containing titanium compounds, with tetraalkoxytitanium compounds being more preferred.
Their dissolution may be accomplished by any publicly known method. The preferred method is contact while stirring in the presence of an inert diluting agent during the dissolution. The inert diluting agent used here is preferably an aliphatic or aromatic hydrocarbon or halohydrocarbon. For the contact there may be included components other than those mentioned above, for example electron donators such as alcohols, ethers, ketones, esters, etc., organic aluminum compounds, halogenated silicon compounds and organic silicon compounds, so long as the effect of the invention is not hindered. The contact temperature is generally about xe2x88x9250xc2x0 C. to 200xc2x0 C. and preferably 0xc2x0 C. to 120xc2x0 C., and the contact time is at least 3 minutes, and preferably 0.5-24 hours.
The amount of the titanium compound used for the dissolution is about 0.01-100, and preferably 0.1-10, in terms of molar ratio with respect to the magnesium compound.
(III) Another specific example of (A-1-2) of the invention is a contact solution of an inorganic magnesium compound and an electron donating compound.
The inorganic magnesium compound used may be a publicly known magnesium compound. Specifically there may be mentioned (a) magnesium dihalides such as MgF2, MgCl2, MgBr2, MgI2, etc.; (b) magnesium alcoholates, for example Mg(OEt)2, Mg(OBu)2, Mg(OPh)2, etc.; (c) halomagnesiumoxy compounds, for example Mg(OH)Cl, Mg(OEt)Cl, Mg(OPh)Cl, etc.; (d) organic acid magnesium salts, for example Mg(OCOCH3)2, Mg(OCOC17H35)2, Mg(OCOC6H5)2, etc., (e) inorganic acid magnesium salts and other compounds, for example Mg(OH)2, MgO, MgCO3, MgSO4, etc. These may also be used in admixture with each other, or may be used as complexes with other compounds in the form of compound salts. Preferred among these are (a) magnesium dihalides and (b) magnesium alcoholates.
Examples of electron donating compounds include oxygen-containing electron donors such as alcohols, phenols, ketones, aldehydes, carboxylic acids, organic acid and inorganic acid esters, ethers, acid amides and acid anhydrides, and nitrogen-containing electron donors such as ammonia, amines, nitriles and isocyanates. Specifically there may be mentioned (a) alcohols, preferably of 1-18 carbon atoms, specifically methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, 2-ethylhexanol, dodecanol, octadecyl alcohol, benzyl alcohol, phenyl ethyl alcohol, etc.; (b) substituted and unsubstituted phenols, for example phenol, cresol, xylenol, ethyl phenol, propyl phenol, nonyl phenol, naphthol, etc.; (c) ketones, preferably of 3-15 carbon atoms, specifically acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.; (d) aldehydes, preferably of 2-15 carbon atoms, specifically acetaldehyde, propionaldehyde, octylaldehyde, benzaldehyde, etc.; (e) organic acid esters, preferably of 2-20 carbon atoms, specifically methyl formate, methyl acetate, ethyl acetate, vinyl acetate, propyl acetate, octyl acetate, cellosolve acetate, ethyl propionate, methyl butyrate, ethyl valerate, ethyl stearate, ethyl chloroacetate, methyl methacrylate, ethyl crotonate, ethyl benzoate, phenyl benzoate, ethyl tolylate, ethyl anisate, dibutyl phthalate, xcex3-butyrolactone, xcex1-valerolactone, ethylene carbonate, etc., and inorganic acid esters, for example trimethyl borate, tetraethyl silicate, tributyl phosphate, tributyl phosphite, etc.; (f) ethers, preferably of 2-20 carbon atoms, specifically methyl ether, ethyl ether, isopropyl ether, butyl ether, isoamyl ether, epichlorhydrin, tetrahydrofuran, dioxane, anisole, etc.; (g) acid amides, for example dimethylformamide, dimethylacetamide, acetamide, benzoic amide, etc.; (h) amines, for example methylamine, ethylamine, diethylamine, triethylamine, tributylamine, piperidine, pyridine, tetramethyl ethylenediamine, etc.; (i) nitriles, for example acetonitrile, benzonitrile, etc. These electron donors may be used in combinations of two or more. Preferred among these are alcohols, ethers and esters, with alcohols being particularly preferred.
Their dissolution may be accomplished by any publicly known method. The preferred method is contact while stirring in the presence of an inert diluting agent during the dissolution. The inert diluting agent used here is preferably an aliphatic or aromatic hydrocarbon or halohydrocarbon. For the contact there may be included components other than those mentioned above, for example titanium compounds, organic aluminum compounds, halogenated silicon compounds and organic silicon compounds, so long as the effect of the invention is not hindered. The contact temperature is generally about xe2x88x9250xc2x0 C. to 200xc2x0 C. and preferably 0xc2x0 C. to 120xc2x0 C., and the contact time is at least 3 minutes, and preferably 0.5-24 hours.
The amount of the electron donating compound used for the dissolution is about 0.01-100, and preferably 0.1-10, in terms of the molar ratio with respect to the magnesium compound.
Component (A-1-3)
(A-1-3) of the invention is a titanium compound. A xe2x80x9ctitanium compoundxe2x80x9d is preferably one which is either soluble or dispersible itself in any of the catalyst preparation processes according to the invention. (Here, xe2x80x9csoluble itselfxe2x80x9d includes compounds solubilized by complexing agent treatment or other treatment of the compound itself.)
As titanium compounds according to the invention there may be mentioned compounds represented by the general formula Ti(OR7)4xe2x88x92pXp (where R7 is a hydrocarbon residue, preferably with about 1-10 carbon atoms, X represents a halogen, and p represents a number such that 0xe2x89xa6pxe2x89xa64). Specifically there may be mentioned TiCl4, TiBr4, Ti(OC2H5)Cl3, Ti(OC2H5)2Cl2, Ti(OC2H5)3Cl, Ti(OiC3H7)Cl3, Ti(OnC4H9)Cl3, Ti(OnC4H9)2Cl2, Ti(OnC4H9)3Cl, Ti(OiC4H9)Cl3, Ti(OsecC4H9)Cl3, Ti(OtC4H9)Cl3, Ti(OC5H11)Cl3, Ti(OC6H13)Cl3, Ti(OC8H17)Cl3, Ti(OcC6H11)Cl3, Ti(OC6H5)Cl3, Ti(OnC4H9)Br3, Ti(OC2H5)4, Ti(OnC3H7)4, Ti(OiC3H7)4, Ti(OnC4H9)4, Ti(OnC6H13)4, Ti(OnC8H17)4, Ti(OCH2CH(C2H5)C4H9)4, etc. There may also be used molecular compounds obtained by reacting electron donors with these. As such molecular compounds there may be mentioned TiCl4.CH3COC2H5, TiCl4.CH3COOC2H5, TiCl4.CH3COCl, TiCl4.C6H5COOC2H5, etc.
Polytitanic acid esters represented by the following general formula may also be used. 
where R8 represents the same or different hydrocarbon residues, preferably with 1-10 carbon atoms. Especially preferred are aliphatic hydrocarbon residues of 2-6 carbon atoms. The value of q is normally such that 2xe2x89xa6qxe2x89xa610.
Specific examples of such compounds include isopropyl polytitanate, normal-butyl polytitanate, normal-hexyl polytitanate and 2-ethylhexyl polytitanate.
There may also be used trivalent titanium compounds represented by the general formula Ti(OR9)3xe2x88x92rXr (where R9 is a hydrocarbon residue, preferably with about 1-10 carbon atoms, X represents a halogen, and r represents a number such that 0xe2x89xa6rxe2x89xa63). Specific examples of such titanium compounds include TiCl3, TiBr3, Ti(OC2H5)Cl2, Ti(OC2H5)3, etc. These may also be used in admixture with each other.
Preferred among these are halogenated titanium compounds and tetraalkoxytitanium compounds.
Component (A-1-4)
(A-1-4) of the invention is a compound selected from among halogenated titanium compounds, halogenated silicon compounds and halogenated aluminum compounds.
As halogenated titanium compounds there may be mentioned compounds represented by the general formula Ti(OR10)4xe2x88x92sXs (where R10 is a hydrocarbon residue, preferably with about 1-10 carbon atoms, X represents a halogen, and s represents a number such that 1xe2x89xa6sxe2x89xa64). Specifically there may be mentioned TiCl4, TiBr4, Ti(OC2H5)Cl3, Ti(OC2H5)2Cl2, Ti(OC2H5)3Cl, Ti(OiC3H7)Cl3, Ti(OnC4H9)Cl3, Ti(OnC4H9)2Cl2, Ti(OnC4H9)3Cl, Ti(OiC4H9)Cl3, Ti (OsecC4H9)Cl3, Ti(OtC4H9)Cl3, Ti(OC5H11)Cl3, Ti(OC6H13)Cl3, Ti(OC8H17)Cl3, Ti(OcC6H11)Cl3, Ti(OC6H5)Cl3, Ti(OnC4H9)Br3, etc. There may also be used molecular compounds obtained by reacting electron donors with these. As such molecular compounds there may be mentioned TiCl4.CH3COC2H5, TiCl4.CH3COOC2H5, TiCl4.CH3COCl, TiCl4.C6H5COOC2H5, etc. There may also be used trivalent titanium compounds represented by the general formula Ti(OR11)3xe2x88x92tXt (where R11 is a hydrocarbon residue, preferably with about 1-10 carbon atoms, X represents a halogen, and t represents a number such that 1xe2x89xa6txe2x89xa63). Specific examples of such titanium compounds include TiCl3, TiBr3, Ti(OC2H5)Cl2, etc.
As halogenated silicon compounds there may be mentioned compounds represented by the general formula Si(OR12)uR13vXw (where R12 and R13 represent the same or different hydrocarbon residues, preferably with about 1-10 carbon atoms, or hydrogen atoms, X represents a halogen, and u, v and w represent numbers such that 0xe2x89xa6uxe2x89xa63, 0xe2x89xa6vxe2x89xa63, and 1xe2x89xa6wxe2x89xa64, provided that u+v+w=4). Specifically there may be mentioned SiCl4, SiBr4, HSiCl3, CH3SiCl3, C2H5SiCl3, C3H7SiCl3, C4H9SiCl3, C8H17SiCl3, C6H5SiCl3, (CH3)2SiCl2, (C2H5)2SiCl2, (C6H5)2SiCl2, (CH3)3SiCl, Si(OCH3)Cl3, Si(OC2H5)Cl3, Si(OC2H5)2Cl2, Si(OC2H5)3Cl, Si(OiC3H7)Cl3, Si(OnC4H9)Cl3, Si(OnC4H9 )2Cl2, Si(OnC4H9)3Cl, Si(OiC4H9Cl3, Si(OsecC4H9)Cl3, Si(OtC4H9)Cl3, Si(OC6H35)Cl5, HSi(OCH3)Cl2, CH3Si(OCH3)Cl2, CH3Si(OC2H5)Cl2, C2H5Si(OCH3)Cl2, (CH3)2Si(OCH3)Cl, etc.
As halogenated aluminum compounds there may be mentioned compounds represented by the general formula AlR14x(OR15)yXz (where R14 and R15 represent the same or different hydrocarbon residues of 1-20 carbon atoms or hydrogen atoms, X represents a halogen, and x, y and z represent numbers such that 0xe2x89xa6x less than 3, 0xe2x89xa6y less than 3, and 0 less than zxe2x89xa63, provided that x+y+z=3). Specifically there may be mentioned diethylaluminum chloride, diisobutylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, ethoxyaluminum dichloride, aluminum trichloride, etc. Any of these within each group and/or of different groups may be used in admixture with each other.
 less than Contact greater than 
Any desired publicly known method may be employed for the contact between component (A-1-1) to component (A-1-3), or between component (A-1-1) to component (A-1-4). The preferred method is contact while stirring in the presence of an inert diluting agent. The inert diluting agent used here is preferably an aliphatic or aromatic hydrocarbon or halohydrocarbon. For the contact there may be included components other than those mentioned above, for example siloxanes, organic aluminum compounds, halogenated silicon compounds and organic silicon compounds, so long as the effect of the invention is not hindered. The contact temperature is generally about xe2x88x9250xc2x0 C. to 200xc2x0 C. and preferably 0xc2x0 C. to 120xc2x0 C., and the treatment time is at least 3 minutes, and preferably 0.5-24 hours.
The ratios for each of the components used for contact are about 0.001-1, and preferably 0.005-0.2, as the weight ratio of Mg atoms in component (A-1-2) with respect to the ion-exchangeable layered silicate of component (A-1-1), and 0.001-50, and preferably 0.01-10, as the molar ratio of Ti atoms in component (A-1-3) with respect to Mg atoms in component (A-1-2). It is about 0.001-50, and preferably 0.01-10, as the molar ratio of Ti, Si or Al atoms in component (A-1-4) with respect to Mg atoms in component (A-1-2). The contact preferably results in the titanium being carried on the ion-exchangeable layered silicate of component (A-1-1) at 0.01-20 wt %, and more preferably 0.1-10 wt %.
 less than  less than Component (A-2) greater than  greater than 
Component (A-2) is a metallocene-type transition metal compound.
The metallocene-type transition metal compound used for the process of the invention is a compound of a transition metal of Group 3-6 of the Periodic Table having one or two cyclopentadienyl-type ligands which may be substituted, or a cationic complex thereof.
Preferred metallocene-type transition metal compounds are compounds represented by the following general formula [1] or [2].
(CpR21aH5xe2x88x92a)c(CpR22bH5xe2x88x92b)dMR23exe2x80x83xe2x80x83[1]
[(CpR21aH5xe2x88x92a)c(CpR22bH5xe2x88x92b)dMR23eLf]g+[R24]gxe2x88x92xe2x80x83xe2x80x83[2]
where CpR21aH5xe2x88x92a and CpR22bH5xe2x88x92b represent cyclopentadienyl (Cp) groups or derivatives thereof.
In the formulas [1] and [2], R21 and R22 are hydrocarbon groups, silicon-containing substituents, phosphorus-containing substituents, nitrogen-containing substituents or oxygen-containing substituents of 1-20 and preferably 1-12 carbon atoms, which may be substituted, and they may be the same or different.
Letters a and b are integers of 0-5. Letters c, d and e are 0 or positive integers satisfying the equation c+d+e=V when the metallocene-type transition metal compound is of formula [1], and are 0 or positive integers satisfying the equation c+d+e=Vxe2x88x92g when the metallocene-type transition metal compound is of formula [2], where V is the valency of M. Normally, c and d are integers of 0-3, and preferably 0 or 1, e is an integer of 0-3 and preferably 1 or 2, and g is an integer that satisfies 0xe2x89xa6gxe2x89xa6V.
As specific examples of R21 and R22 there may be mentioned (a) alkyl groups, for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, etc.; (b) aryl groups, for example phenyl, p-tolyl, o-tolyl, m-tolyl, etc.; (c) halo-substituted hydrocarbon groups, for example fluoromethyl, fluoroethyl, fluorophenyl, chloromethyl, chloroethyl, chlorophenyl, bromomethyl, bromoethyl, bromophenyl, iodomethyl, iodoethyl, iodophenyl, etc.; (d) silicon-containing substituents, for example trimethylsilyl, triethylsilyl, triphenylsilyl, etc.; (e) alkoxy groups, for example methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, etc.; (f) aryloxy groups, for example phenoxy, methylphenoxy, pentamethylphenoxy, p-tolyloxy, o-tolyloxy, m-tolyloxy, etc. Preferred among these are alkyl groups of 1-4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, etc., trimethylsilyl, alkoxy groups such as methoxy, etc., and aryloxy groups such as phenoxy, etc.
When two cyclopentadienyl (Cp) groups are present in the same compound, the Cp groups may be bonded together via a crosslinking group to form a crosslinked structure (in which case, the crosslinking group may be considered as a bonded group between one R21 and one R22). As such crosslinking groups there may be mentioned (a) alkylene groups, for example methylene and ethylene; (b) alkylidene groups, for example ethylidene, propylidene, isopropylidene, phenylmethylidene and diphenylmethylidene; (c) silicon-containing crosslinking groups, for example dimethylsilylene, diethylsilylene, dipropylsilylene, diisopropylsilylene, diphenylsilylene, methylethylsilylene, methylphenylsilylene, methylisopropylsilylene and methyl-t-butylsilylene; (d) germanium-containing crosslinking groups, for example dimethylgermylene, diethylgermylene, dipropylgermylene, diisopropylgermylene, diphenylgermylene, methylethylgermylene, methylphenylgermylene, methylisopropylgermylene and methyl-t-butylgermylene; (e) nitrogen-containing crosslinking groups, for example amino groups, etc.; (f) phosphorus-containing crosslinking groups, for example phosphinyl, etc.
More than one R21 or R22 may also be bonded together to form a ring. A typical such case is a structure wherein two R21 (or R22) groups bonded to adjacent carbon atoms of the same Cp group are bonded together, and specifically there may be mentioned indenyl, tetrahydroindenyl, fluorenyl, octahydrofluorenyl, etc. as preferred ones. These may also be substituted.
R23 is a hydrocarbon group of 1 to 20, and preferably 1-10 carbon atoms which may be substituted, hydrogen, a halogen, a silicon-containing substituent, an alkoxy group, an aryloxy group, an amido group or a thioalkoxy group. Specifically there may be mentioned (a) alkyl groups, for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, etc.; (b) aryl groups, for example phenyl, p-tolyl, o-tolyl, m-tolyl, etc.; (c) halo-substituted hydrocarbon groups, for example fluoromethyl, fluoroethyl, fluorophenyl, chloromethyl, chloroethyl, chlorophenyl, bromomethyl, bromoethyl, bromophenyl, iodomethyl, iodoethyl, iodophenyl, etc.; (d) halogens, for example fluorine, chlorine, bromine, iodine, etc.; (e) silicon-containing substituents, for example trimethylsilyl, triethylsilyl, triphenylsilyl, etc.; (f) alkoxy groups, for example methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, etc.; (g) aryloxy groups, for example phenoxy, methylphenoxy, pentamethylphenoxy, p-tolyloxy, m-tolyloxy, o-tolyloxy, etc.; (h) amido groups, for example dimethylamido, diethylamido, dipropylamido, diisopropylamido, ethyl-t-butylamido, bis(trimethylsilyl)amido, etc.; (i) thioalkoxy groups, for example methylthioalkoxy, ethylthioalkoxy, propylthioalkoxy, butylthioalkoxy, t-butylthioalkoxy, phenylthioalkoxy, etc. Preferred among these are hydrogen, methyl, ethyl, propyl, isopropyl, butyl, phenyl, halogens such as chlorine, methoxy, ethoxy, propoxy, isopropoxy, dimethylamido and methylthioalkoxy, of which hydrogen, methyl and chlorine are especially preferred.
R23 may be bonded with R21, R22 or Cp, and as specific examples of such ligands there may be mentioned CpH4(CH2)hOxe2x80x94 (1xe2x89xa6hxe2x89xa65), CpMe4(CH2)iOxe2x80x94 (1xe2x89xa6ixe2x89xa65), CpH4(Me2Si)(t-Bu)Nxe2x80x94, CpMe4(Me2Si)(t-Bu)Nxe2x80x94, etc. (where Cp represents cyclopentadienyl, Me represents methyl and Bu represents butyl). More than one R23 may also be bonded together to form a bidentate ligand. As specific examples of this type of R23 there may be mentioned xe2x80x94OCH2Oxe2x80x94, xe2x80x94OCH2CH2Oxe2x80x94, xe2x80x94O(oxe2x80x94C6H4)Oxe2x80x94, etc.
M is an atom of Group 3, 4, 5 or 6 of the Periodic Table, and specifically there may be mentioned scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, actinium, thorium, protoactinium, uranium, titanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium, molybdenum and tungsten. Among these, titanium, zirconium and hafnium of Group 4 are preferred for use. These may also be used in combination.
L represents an electrically neutral ligand of which f is the number representing an integer of 0 or greater, and specifically there may be mentioned ethers such as diethyl ether, tetrahydrofuran and dioxane, nitrites such as acetonitrile, amides such as dimethylformamide, phosphines such as trimethylphosphine and amines such as trimethylamine. Tetrahydrofuran, trimethylphosphine and trimethylamine are preferred.
[R24]gxe2x88x92 represents one or more anions that neutralize the cation, and specifically there may be mentioned tetraphenylborate, tetra(p-tolyl)borate, carbadodecaborate, dicarbaundecaborate, tetrakis(pentafluorophenyl)borate, tetrafluoroborate, hexafluorophosphate, etc. Preferred are tetraphenylborate, tetra(p-tolyl)borate, tetrakis(pentafluorophenyl)borate, tetrafluoroborate and hexafluorophosphate.
Specific examples of the aforementioned metallocene-type transition metal compound are listed below. The following correspond to formula [1] where zirconium is used:
(1) bis(methylcyclopentadienyl)zirconium dichloride,
(2) bis(ethylcyclopentadienyl)zirconium dichloride,
(3) bis(methylcyclopentadienyl)zirconium dimethyl,
(4) bis(ethylcyclopentadienyl)zirconium dimethyl,
(5) bis(methylcyclopentadienyl)zirconium dihydride,
(6) bis(ethylcyclopentadienyl)zirconium dihydride,
(7) bis(dimethylcyclopentadienyl)zirconium dichloride,
(8) bis(trimethylcyclopentadienyl)zirconium dichloride,
(9) bis(tetramethylcyclopentadienyl)zirconium dichloride,
(10) bis(ethyltetramethylcyclopentadienyl)zirconium dichloride,
(11) bis(indenyl)zirconium dichloride,
(12) bis(dimethylcyclopentadienyl)zirconium dimethyl,
(13) bis(trimethylcyclopentadienyl)zirconium dimethyl,
(14) bis(tetramethylcyclopentadienyl)zirconium dimethyl,
(15) bis(ethyltetramethylcyclopentadienyl)zirconium dimethyl,
(16) bis(indenyl)zirconium dimethyl,
(17) bis(dimethylcyclopentadienyl)zirconium dihydride,
(18) bis(trimethylcyclopentadienyl)zirconium dihydride,
(19) bis(ethyltetramethylcyclopentadienyl)zirconium dihydride,
(20) bis(trimethylsilylcyclopentadienyl)zirconium dimethyl,
(21) bis(trimethylsilylcyclopentadienyl)zirconium dihydride,
(22) bis(trifluoromethylcyclopentadienyl)zirconium dichloride,
(23) bis(trifluoromethylcyclopentadienyl)zirconium dimethyl,
(24) bis(trifluoromethylcyclopentadienyl)zirconium dihydride,
(25) isopropylidene-bis(indenyl)zirconium dichloride,
(26) isopropylidene-bis(indenyl)zirconium dimethyl,
(27) isopropylidene-bis(indenyl)zirconium dihydride,
(28) pentamethylcyclopentadienyl(cyclopentadienyl)zirconium dichloride,
(29) pentamethylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl,
(30) pentamethylcyclopentadienyl(cyclopentadienyl)zirconium dihydride,
(31) ethyltetramethylcyclopentadienyl(cyclopentadienyl) zirconium dihydride,
(32) isopropylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride,
(33) isopropylidene(cyclopentadienyl)(fluorenyl)zirconium dimethyl,
(34) dimethylsilyl(cyclopentadienyl)(fluorenyl)zirconium dimethyl,
(35) isopropylidene(cyclopentadienyl)(fluorenyl)zirconium dihydride,
(36) bis(cyclopentadienyl)zirconium dichloride,
(37) bis(cyclopentadienyl)zirconium dimethyl,
(38) bis(cyclopentadienyl)zirconium diethyl,
(39) bis(cyclopentadienyl)zirconium dipropyl,
(40) bis(cyclopentadienyl)zirconium diphenyl,
(41) methylcyclopentadienyl(cyclopentadienyl)zirconium dichloride,
(42) ethylcyclopentadienyl(cyclopentadienyl)zirconium dichloride,
(43) methylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl,
(44) ethylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl,
(45) methylcyclopentadienyl(cyclopentadienyl)zirconium dihydride,
(46) ethylcyclopentadienyl(cyclopentadienyl)zirconium dihydride,
(47) dimethylcyclopentadienyl(cyclopentadienyl)zirconium dichloride,
(48) trimethylcyclopentadienyl(cyclopentadienyl)zirconium dichloride,
(49) tetramethylcyclopentadienyl(cyclopentadienyl)zirconium dichloride,
(50) bis(pentamethylcyclopentadienyl)zirconium dichloride,
(51) tetramethylcyclopentadienyl(cyclopentadienyl)zirconium dichloride,
(52) indenyl(cyclopentadienyl)zirconium dichloride,
(53) dimethylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl,
(54) trimethylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl,
(55) tetramethylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl,
(56) bis(pentamethylcyclopentadienyl)zirconium dimethyl,
(57) ethyltetramethylcyclopentadienyl(cyclopentadienyl) zirconium dimethyl,
(58) indenyl(cyclopentadienyl)zirconium dimethyl,
(59) dimethylcyclopentadienyl(cyclopentadienyl)zirconium dihydride,
(60) trimethylcyclopentadienyl(cyclopentadienyl)zirconium dihydride,
(61) bis(pentamethylcyclopentadienyl)zirconium dihydride,
(62) indenyl( cyclopentadienyl)zirconium dihydride,
(63) trimethylsilylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl,
(64) trimethylsilylcyclopentadienyl(cyclopentadienyl)zirconium dihydride,
(65) trifluoromethylcyclopentadienyl(cyclopentadienyl)zirconium dichloride,
(66) trifluoromethylcyclopentadienyl(cyclopentadienyl)zirconium dimethyl,
(67) trifluoromethylpentadienyl(cyclopentadienyl)zirconium dihydride,
(68) bis(cyclopentadienyl)(trimethylsilyl)(methyl)zirconium,
(69) bis(cyclopentadienyl)(triphenylsilyl)(methyl)zirconium,
(70) bis(cyclopentadienyl)[tris(trimethylsilyl)silyl] (methyl)zirconium,
(71) bis(cyclopentadienyl)[bis(methylsilyl)silyl](methyl)zirconium,
(72) bis(cyclopentadienyl)(trimethylsilyl)(trimethylsilylmethyl)zirconium,
(73) bis(cyclopentadienyl)(trimethylsilyl)(benzyl)zirconium,
(74) methylene-bis(cyclopentadienyl)zirconium dichloride,
(75) ethylene-bis(cyclopentadienyl)zirconium dichloride,
(76) isopropylidene-bis(cyclopentadienyl)zirconium dichloride,
(77) dimethylsilyl-bis(cyclopentadienyl)zirconium dichloride,
(78) methylene-bis(cyclopentadienyl)zirconium dimethyl,
(79) ethylene-bis(cyclopentadienyl)zirconium dimethyl,
(80) isopropylidene-bis(cyclopentadienyl)zirconium dimethyl,
(81) dimethylsilyl-bis(cyclopentadienyl)zirconium dimethyl,
(82) methylene-bis(cyclopentadienyl)zirconium dihydride,
(83) ethylene-bis(cyclopentadienyl)zirconium dihydride,
(84) isopropylidene-bis(cyclopentadienyl)zirconium dihydride,
(85) dimethylsilyl-bis(cyclopentadienyl)zirconium dihydride,
(86) bis(cyclopentadienyl)zirconium bis(methanesulfonate),
(87) bis(cyclopentadienyl)zirconium bis(p-toluenesulfonate),
(88) bis(cyclopentadienyl)zirconium bis(trifluoromethanesulfonate),
(89) bis(cyclopentadienyl)zirconium trifluoromethanesulfonate chloride,
(90) bis(cyclopentadienyl)zirconium bis(benzenesulfonate),
(91) bis(cyclopentadienyl)zirconium bis(pentafluorobenzenesulfonate),
(92) bis(cyclopentadienyl)zirconium benzenesulfonate chloride,
(93) bis(cyclopentadienyl)zirconium(ethoxy)trifluoromethanesulfonate,
(94) bis(tetramethylcyclopentadienyl)zirconium bis(trifluoromethanesulfonate),
(95) bis(indenyl)zirconium bis(trifluoromethanesulfonate),
(96) ethylene-bis(indenyl)zirconium bis(trifluoromethanesulfonate),
(97) isopropylidene-bis(indenyl)zirconium bis(trifluoromethanesulfonate),
(98) (tertiary butylamido)dimethyl(tetramethylcyclopentadienyl)silane dibenzyl zirconium,
(99) (tertiary butylamido)dimethyl (2,3,4,5-tetramethylcyclopentadienyl)silane dibenzyl zirconium,
(100) indenyl zirconium tris(dimethylamide),
(101) indenyl zirconium tris(diethylamide),
(102) indenyl zirconium tris(di-n-propylamide),
(103) cyclopentadienyl zirconium tris(dimethylamide),
(104) methylcyclopentadienyl zirconium tris(dimethylamide),
(105) (tertiary butylamido)(tetramethylcyclopentadienyl)-1, 2-ethandiyl zirconium dichloride,
(106) (methylamido)-(tetramethylcyclopentadienyl)-1,2-ethandiyl zirconium dichloride,
(107) (ethylamido)(tetramethylcyclopentadienyl)methylene zirconium dichloride,
(108) (tertiary butylamido)dimethyl(tetramethylcyclopentadienyl)silane zirconium dichloride,
(109) (benzylamido)dimethyl(tetramethylcyclopentadienyl)silane zirconium dichloride,
(110) (phenylphosphido)dimethyl(tetramethylcyclopentadienyl)silane zirconium dibenzyl,
(111) (phenylamido)dimethyl(tetramethylcyclopentadienyl)silane zirconium dichloride,
(112) (2-methoxyphenylamido)dimethyl(tetramethylcyclopentadienyl)silane zirconium dichloride,
(113) (4-fluorophenylamido)dimethyl(tetramethylcyclopentadienyl)silane zirconium dichloride,
(114) ((2,6-di(1-methylethyl)phenyl)amido)methyl(tetramethylcyclopentadienyl)silane zirconium dichloride, etc.
(115) bis(n-butylcyclopentadienyl)zirconium dichloride,
(116) bis(n-butylcyclopentadienyl)zirconium dimethyl,
(117) bis(n-butylcyclopentadienyl)zirconium dihydride,
(118) bis(methyl, n-butylcyclopentadienyl)zirconium dichloride,
(119) bis(methyl, n-butylcyclopentadienyl)zirconium dimethyl,
(120) bis(methyl, n-butylcyclopentadienyl)zirconium dihydride,
(121) methylene-bis(indenyl)zirconium dichloride,
(122) methylene-bis(indenyl)zirconium dimethyl,
(123) methylene-bis(indenyl)zirconium dihydride,
(124) ethylene-bis(indenyl)zirconium dichloride,
(125) ethylene-bis(indenyl)zirconium dimethyl,
(126) ethylene-bis(indenyl)zirconium dihydride,
(127) ethylene-bis(4,5,6,7-tetrahydroindenyl)zirconium dichloride,
(128) ethylene-bis(4,5,6,7-tetrahydroindenyl)zirconium dimethyl,
(129) ethylene-bis(4,5,6,7-tetrahydroindenyl)zirconium dihydride,
(130) dimethylsilyl-bis(indenyl)zirconium dichloride,
(131) dimethylsilyl-bis(indenyl)zirconium dimethyl,
(132) dimethylsilyl-bis(indenyl)zirconium dihydride,
(133) dimethylsilyl-bis(2-methylindenyl)zirconium dichloride,
(134) dimethylsilyl-bis(2-methylindenyl)zirconium dimethyl,
(135) dimethylsilyl-bis(2-methylindenyl)zirconium dihydride,
(136) dimethylsilyl-bis(2-methyl,4-phenylindenyl)zirconium dichloride,
(137) dimethylsilyl-bis(2-methyl,4-phenylindenyl)zirconium dimethyl,
(138) dimethylsilyl-bis(2-methyl,4-phenylindenyl)zirconium dihydride,
(139) dimethylsilyl-bis(2-methylbenzoindenyl)zirconium dichloride,
(140) dimethylsilyl-bis(2-methylbenzoindenyl)zirconium dimethyl,
(141) dimethylsilyl-bis(2-methylbenzoindenyl)zirconium dihydoride,
(142) dimethylsilyl-bis(2-methyl,4-phenylazulenyl)zirconium dichloride,
(143) dimethylsilyl-bis(2-methyl,4-phenylazulenyl)zirconium dimethyl,
(144) dimethylsilyl-bis(2-methyl,4-phenylazulenyl)zirconium dihydoride,
The following correspond to formula [2] where zirconium is used:
(1) bis(methylcyclopentadienyl)zirconium(chloride)(tetraphenylborate)tetrahydrofuran complex,
(2) bis(ethylcyclopentadienyl)zirconium(chloride)(tetraphenylborate)tetrahydrofuran complex,
(3) bis(methylcyclopentadienyl)zirconium(methyl)(tetraphenylborate)tetrahydrofuran complex,
(4) bis(ethylcyclopentadienyl)zirconium(methyl)(tetraphenylborate)tetrahydrofuran complex,
(5) bis(methylcyclopentadienyl)zirconium(hydride)(tetraphenylborate)tetrahydrofuran complex,
(6) bis(ethylcyclopentadienyl)zirconium(hydride)(tetraphenylborate)tetrahydrofuran complex,
(7) bis(dimethylcyclopentadienyl)zirconium(chloride)(tetraphenylborate)tetrahydrofuran complex,
(8) bis(trimethylcyclopentadienyl)zirconium(chloride)(tetraphenylborate)tetrahydrofuran complex,
(9) bis(tetramethylcyclopentadienyl)zirconium(chloride)(tetraphenylborate)tetrahydrofuran complex,
(10) bis(ethyltetramethylcyclopentadienyl)zirconium(chloride)(tetraphenylborate)tetrahydrofuran complex,
(11) bis(indenyl)zirconium(chloride)(tetraphenylborate)tetrahydrofuran complex,
(12) bis(dimethylcyclopentadienyl)zirconium(methyl)(tetraphenylborate)tetrahydrofuran complex,
(13) bis(trimethylcyclopentadienyl)zirconium(methyl)(tetraphenylborate)tetrahydrofuran complex,
(14) bis(tetramethylcyclopentadienyl)zirconium(methyl)(tetraphenylborate)tetrahydrofuran complex,
(15) bis(ethyltetramethylcyclopentadienyl)zirconium(methyl)(tetraphenylborate)tetrahydrofuran complex,
(16) bis(indenyl)zirconium(methyl)(tetraphenylborate)tetrahydrofuran complex,
(17) bis(dimethylcyclopentadienyl)zirconium(hydride)(tetraphenylborate)tetrahydrofuran complex,
(18) bis(trimethylcyclopentadienyl)zirconium(hydride)(tetraphenylborate)tetrahydrofuran complex,
(19) bis(ethyltetramethylcyclopentadienyl)zirconium(hydride)(tetraphenylborate)tetrahydrofuran complex,
(20) bis(trimethylsilylcyclopentadienyl)zirconium(methyl)(tetraphenylborate)tetrahydrofuran complex,
(21) bis(trimethylsilylcyclopentadienyl)zirconium(hydride)(tetraphenylborate)tetrahydrofuran complex,
(22) bis(trifluoromethylcyclopentadienyl)zirconium(methyl)(tetraphenylborate)tetrahydrofuran complex,
(23) bis(trifluoromethylcyclopentadienyl)zirconium(hydride)(tetraphenylborate)tetrahydrofuran complex,
(24) isopropylidene-bis(indenyl)zirconium(chloride)(tetraphenylborate)tetrahydrofuran complex,
(25) isopropylidene-bis(indenyl)zirconium(methyl)(tetraphenylborate)tetrahydrofuran complex,
(26) isopropylidene-bis(indenyl)zirconium(hydride)(tetraphenylborate)tetrahydrofuran complex,
(27) pentamethylcyclopentadienyl(cyclopentadienyl)zirconium(chloride)(tetraphenylborate)tetrahydrofuran complex,
(28) ethyltetramethylcyclopentadienyl(cyclopentadienyl)zirconium(chloride)(tetraphenylborate)tetrahydrofuran complex,
(29) pentamethylcyclopentadienyl(cyclopentadienyl)zirconium(methyl)(tetraphenylborate)tetrahydrofuran complex,
(30) ethyltetramethylcyclopentadienyl(cyclopentadienyl)zirconium(methyl)(tetraphenylborate)tetrahydrofuran complex,
(31) pentamethylcyclopentadienyl(cyclopentadienyl)zirconium(hydride)(tetraphenylborate)tetrahydrofuran complex,
(32) ethyltetramethylcyclopentadienyl(cyclopentadienyl)zirconium(hydride)(tetraphenylborate)tetrahydrofuran complex,
(33) isopropylidene(cyclopentadienyl)(fluorenyl)zirconium(chloride)(tetraphenylborate)tetrahydrofuran complex,
(34) isopropylidene(cyclopentadienyl)(fluorenyl)zirconium(methyl)(tetraphenylborate)tetrahydrofuran complex,
(35) isopropylidene(cyclopentadienyl)(fluorenyl)zirconium(hydride)(tetraphenylborate)tetrahydrofuran complex,
(36) bis(cyclopentadienyl)zirconium(chloride)(tetraphenylborate)tetrahydrofuran complex,
(37) bis(cyclopentadienyl)zirconium(methyl)(tetraphenylborate)tetrahydrofuran complex,
(38) bis(cyclopentadienyl)zirconium(ethyl)(tetraphenylborate)tetrahydrofuran complex,
(39) bis(cyclopentadienyl)zirconium(propyl)(tetraphenylborate)tetrahydrofuran complex,
(40) bis(cyclopentadienyl)zirconium (phenyl)(tetraphenylborate)tetrahydrofuran complex,
(41) methylcyclopentadienyl(cyclopentadienyl)zirconium(chloride)(tetraphenylborate)tetrahydrofuran complex,
(42) ethylcyclopentadienyl(cyclopentadienyl)zirconium(chloride)(tetraphenylborate)tetrahydrofuran complex,
(43) bis(ethylcyclopentadienyl)zirconium(chloride)(tetraphenylborate)tetrahydrofuran complex,
(44) methylcyclopentadienyl(cyclopentadienyl)zirconium(methyl)(tetraphenylborate)tetrahydrofuran complex,
(45) ethylcyclopentadienyl(cyclopentadienyl)zirconium(methyl)(tetraphenylborate)tetrahydrofuran complex,
(46) methylcyclopentadienyl(cyclopentadienyl)zirconium(hydride)(tetraphenylborate)tetrahydrofuran complex,
(47) ethylcyclopentadienyl(cyclopentadienyl)zirconium(hydride)(tetraphenylborate)tetrahydrofuran complex,
(48) dimethylcyclopentadienyl(cyclopentadienyl)zirconium(chloride)(tetraphenylborate)tetrahydrofuran complex,
(49) trimethylcyclopentadienyl(cyclopentadienyl)zirconium(chloride)(tetraphenylborate)tetrahydrofuran complex,
(50)tetramethylcyclopentadienyl(cyclopentadienyl)zirconium(chloride)(tetraphenylborate)tetrahydrofuran complex,
(51) bis(pentamethylcyclopentadienyl)zirconium(chloride)(tetraphenylborate)tetrahydrofuran complex,
(52) indenyl(cyclopentadienyl)zirconium(chloride)(tetraphenylborate)tetrahydrofuran complex,
(53) dimethylcyclopentadienyl(cyclopentadienyl)zirconium(methyl)(tetraphenylborate)tetrahydrofuran complex,
(54) trimethylcyclopentadienyl(cyclopentadienyl)zirconium(methyl)(tetraphenylborate)tetrahydrofuran complex,
(55)tetramethylcyclopentadienyl(cyclopentadienyl)zirconium(methyl)(tetraphenylborate)tetrahydrofuran complex,
(56) bis(pentamethylcyclopentadienyl)zirconium(methyl)(tetraphenylborate)tetrahydrofuran complex,
(57) cyclopentadienyl(indenyl)zirconium(methyl)(tetraphenylborate)tetrahydrofuran complex,
(58) dimethylcyclopentadienyl(cyclopentadienyl)zirconium(hydride)(tetraphenylborate)tetrahydrofuran complex,
(59) trimethylcyclopentadienyl(cyclopentadienyl)zirconium(hydride)(tetraphenylborate)tetrahydrofuran complex,
(60) bis(pentamethylcyclopentadienyl)zirconium(hydride)(tetraphenylborate)tetrahydrofuran complex,
(61) indenyl(cyclopentadienyl)zirconium(hydride)(tetraphenylborate)tetrahydrofuran complex,
(62) trimethylsilylcyclopentadienyl(cyclopentadienyl)zirconium(methyl)(tetraphenylborate)tetrahydrofuran complex,
(63) trimethylsilylcyclopentadienyl(cyclopentadienyl)zirconium(hydride)(tetraphenylborate)tetrahydrofuran complex,
(64) trifluoromethylcyclopentadienyl(cyclopentadienyl)zirconium(hydride)(tetraphenylborate)tetrahydrofuran complex,
(65) bis(cyclopentadienyl)(trimethylsilyl)zirconium(tetraphenylborate)tetrahydrofuran complex,
(66) bis(cyclopentadienyl)(triphenylsilyl)zirconium(tetraphenylborate)tetrahydrofuran complex,
(67) bis(cyclopentadienyl)[tris(trimethylsilyl)silyl]zirconium(tetraphenylborate)tetrahydrofuran complex,
(68) bis(cyclopentadienyl)(trimethylsilylmethyl)zirconium(tetraphenylborate)tetrahydrofuran complex,
(69) bis(cyclopentadienyl)(benzyl)zirconium(tetraphenylborate)tetrahydrofuran complex,
(70) methylene-bis(cyclopentadienyl)zirconium(chloride)(tetraphenylborate)tetrahydrofuran complex,
(71) ethylene-bis(cyclopentadienyl)zirconium(chloride)(tetraphenylborate)tetrahydrofuran complex,
(72) isopropylidene-bis(cyclopentadienyl)zirconium(chloride)(tetraphenylborate)tetrahydrofuran complex,
(73) dimethylsilyl-bis(cyclopentadienyl)zirconium(chloride)(tetraphenylborate)tetrahydrofuran complex,
(74) methylene-bis(cyclopentadienyl)zirconium(methyl)(tetraphenylborate)tetrahydrofuran complex,
(75) ethylene-bis(cyclopentadienyl)zirconium(methyl)(tetraphenylborate)tetrahydrofuran complex,
(76) isopropylidene-bis(cyclopentadienyl)zirconium(methyl)(tetraphenylborate)tetrahydrofuran complex,
(77) dimethylsilyl-bis(cyclopentadienyl)zirconium(methyl)(tetraphenylborate)tetrahydrofuran complex,
(78) methylene-bis(cyclopentadienyl)zirconium(hydride)(tetraphenylborate)tetrahydrofuran complex,
(79) ethylene-bis(cyclopentadienyl)zirconium(hydride)(tetraphenylborate)tetrahydrofuran complex,
(80) isopropylidene-bis(cyclopentadienyl)zirconium(hydride)(tetraphenylborate)tetrahydrofuran complex,
(81) dimethylsilyl-bis(cyclopentadienyl)zirconium(hydride)(tetraphenylborate)tetrahydrofuran complex,
(82) bis(cyclopentadienyl)zirconium(methanesulfonate)(tetraphenylborate)tetrahydrofuran complex,
(83) bis(cyclopentadienyl)zirconium(p-toluenesulfonate)(tetraphenylborate)tetrahydrofuran complex,
(84) bis(cyclopentadienyl)zirconium(trifluoromethanesulfonate)(tetraphenylborate)tetrahydrofuran complex,
(85) bis(cyclopentadienyl)zirconium(benzenesulfonate)(tetraphenylborate)tetrahydrofuran complex,
(86) bis(cyclopentadienyl)zirconium(pentafluorobenzenesulfonate)(tetraphenylborate)tetrahydrofuran complex,
(87) bis(tetramethylcyclopentadienyl)zirconium(trifluoromethanesulfonate)(tetraphenylborate)tetrahydrofuran complex,
(88) bis(indenyl)zirconium(trifluoromethanesulfonate)(tetraphenylborate)tetrahydrofuran complex,
(89) ethylenebis(indenyl)zirconium(trifluoromethanesulfonate)(tetraphenylborate)tetrahydrofuran complex,
(90) isopropylidene-bis(indenyl)zirconium(trifluoromethanesulfonate)(tetraphenylborate)tetrahydrofuran complex, etc.
In the examples mentioned above, disubstituents of the cyclopentadienyl ring include 1,2- and 1,3-substituents, and trisubstituents include 1,2,3- and 1,2,4-substituents.
There may also be mentioned compounds similar to those listed above, using compounds of other metals of Groups 3, 4, 5 and 6, such as titanium compounds and hafnium compounds. Mixtures of these compounds may also be used.
 less than  less than Preparation of Component (A) greater than  greater than 
Component (A) of the invention comprises the above-mentioned component (A-1) and component (A-2). Component (A) can be obtained by contacting these two components outside of the reaction system, or it may be synthesized inside the system. When the two components are contacted, there may be employed, for example, a mechanical mixing method using a revolving ball mill, oscillating mill, jet mill, medium agitating pulverizer or the like, a method of contact by agitation in the presence of an inert diluting agent, or a method of forced carrying by co-drying or co-precipitation. The inert solvent used here is preferably an aliphatic, alicyclic or aromatic hydrocarbon or halohydrocarbon compound. The contact may be carried out in any desired order.
For the contact, there may be included components other than those mentioned above, for example organic aluminum compounds, organometallic compounds, organic silicon compounds, siloxanes and halogenated silicon compounds, so long as the effect of the invention is not hindered. The contact temperature is usually about xe2x88x9250xc2x0 C. to 200xc2x0 C. The amount of the components used for the contact is in the range of 0.0001-10 mmol, and preferably 0.001-5 mmol of component (A-2) to 1 gram of component (A-1).
Component (A) can be subjected to pre-polymerization treatment which comprises polymerizing a small amount of an ethylenic unsaturated compound in the presence of an organic aluminum compound. The organic aluminum compound used therefor may be, specifically, component (B) described below. The ethylenic unsaturated compound used may be, specifically, xcex1-olefins such as ethylene, propylene, butene, pentene, hexene, etc., styrenes such as styrene, divinylbenzene, etc., dienes such as butadiene, isoprene, 1,9-decadiene, 1,7-octadiene, etc., or cyclic olefins such as cyclopentene, norbornene, etc. The pre-polymerization is preferably carried out to produce about 0.01-1000 g, and preferably 0.1-100 g of polymer per 1 gram of the solid catalyst component (A).
 less than Component (B)/organic Aluminum Compound greater than 
Component (B) is an organic aluminum compound.
The organic aluminum compound used for the invention may be a compound represented by the general formula Rxe2x80x23xe2x88x92hAlXh or Rxe2x80x23xe2x88x92iAl(ORxe2x80x3)i (where Rxe2x80x2 and Rxe2x80x3 are hydrocarbon residues of 1-20 carbon atoms, or hydrogen atoms, X is a halogen, and h and i are such that 0xe2x89xa6h less than 3 and 0xe2x89xa6i less than 3). Specific examples include (a) trialkylaluminums, for example trimethylaluminum, triethylaluminum, tripropylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum, etc.; (b) alkylaluminum halides, for example diethylaluminum chloride, diisobutylaluminum chloride, ethylaluminum sesquichloride, ethylaluminum dichloride, etc.; (c) alkylaluminum hydrides, for example diethylaluminum hydride, diisobutylaluminum hydride, etc.; and (d) alkylaluminum alkoxides, for example diethylaluminum ethoxide, diethylaluminum phenoxide, etc. There may also be used (e) alumoxanes, for example methylalumoxane, isobutylalumoxane, etc. These may also be used in combinations of two or more. Preferred among these are trialkylaluminums.
These are generally used in an amount such that the proportion is Al/M=0.1-100,000 mole/mole, and preferably Al/M=1-10,000 mole/mole, as the ratio with the metallocene-type transition metal compound in the solid catalyst component (A).
[Olefin Polymerization]
A publicly known olefin polymerization process may be employed for production of a polymer according to the invention. That is, it may be carried out with a batch system, a continuous system or a semi-batch system. It may also be carried out by a polymerization process wherein the medium is an inert hydrocarbon such as propane, butane, pentane, hexane, heptane, toluene or cyclohexane, by a polymerization process wherein the used monomer itself is the medium, or by a polymerization process in a gas phase using no medium.
The olefin polymerized by the polymerization process of the invention is represented by the general formula R30xe2x80x94CHxe2x95x90CH2 (where R30 represents a hydrogen atom or a hydrocarbon residue of 1-10 carbon atoms), and specific examples thereof include olefins such as ethylene, propylene, 1-butene, 1-pentene, 3-methylbutene-1,1-hexene, 4-methylpentene-1,1-octene, styrene, etc. These may be used in combination with each other for random copolymerization or block copolymerization.
The process of the invention may be used to produce isotactic polymers, syndiotactic polymers or atactic polymers.
The polymerization conditions are in the range of a polymerization temperature of 0-280xc2x0 C., and preferably 50-250xc2x0 C., and a polymerization pressure of normally 1-2000 kg/cm2G. If necessary, the molecular weight may be controlled for the polymerization by using a molecular weight adjuster such as hydrogen.